JPH04202436A - Biodegradable film - Google Patents
Biodegradable filmInfo
- Publication number
- JPH04202436A JPH04202436A JP33605890A JP33605890A JPH04202436A JP H04202436 A JPH04202436 A JP H04202436A JP 33605890 A JP33605890 A JP 33605890A JP 33605890 A JP33605890 A JP 33605890A JP H04202436 A JPH04202436 A JP H04202436A
- Authority
- JP
- Japan
- Prior art keywords
- film
- cellulose
- chitosan
- rice starch
- strength
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000001913 cellulose Substances 0.000 claims abstract description 29
- 229920001661 Chitosan Polymers 0.000 claims abstract description 27
- 229940100486 rice starch Drugs 0.000 claims abstract description 19
- 229920002678 cellulose Polymers 0.000 claims abstract description 18
- 235000010980 cellulose Nutrition 0.000 claims abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229920003124 powdered cellulose Polymers 0.000 claims abstract description 11
- 235000019814 powdered cellulose Nutrition 0.000 claims abstract description 11
- 239000008187 granular material Substances 0.000 claims description 12
- 239000002245 particle Substances 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 6
- 239000011550 stock solution Substances 0.000 description 17
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 12
- 238000001035 drying Methods 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 7
- 229920003043 Cellulose fiber Polymers 0.000 description 6
- 235000011187 glycerol Nutrition 0.000 description 6
- 239000002689 soil Substances 0.000 description 5
- 229920002472 Starch Polymers 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000006196 deacetylation Effects 0.000 description 4
- 238000003381 deacetylation reaction Methods 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 235000019698 starch Nutrition 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000013535 sea water Substances 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- 229920002261 Corn starch Polymers 0.000 description 2
- 241000238557 Decapoda Species 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000008120 corn starch Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229930014626 natural product Natural products 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 229920002101 Chitin Polymers 0.000 description 1
- 241000238424 Crustacea Species 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 101100145155 Escherichia phage lambda cIII gene Proteins 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000850 deacetylating effect Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 210000001724 microfibril Anatomy 0.000 description 1
- 108700005457 microfibrillar Proteins 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000013502 plastic waste Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001592 potato starch Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
Landscapes
- Biological Depolymerization Polymers (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、セルロースおよび／またはデンプンとキトサ
ンからなる、優れたフィルム強度および生分解性を有す
るフィルムに関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a film comprising cellulose and/or starch and chitosan and having excellent film strength and biodegradability.
〔従来の技術］
近年、プラス千ンク廃棄物による環境汚染が重大な社会
的問題となっている。すなわち、包装材料をはじめとし
て、様々な用途に多量に使用されているプラスチックは
、優れた機械的強度、耐久性を有している反面、使用後
に自然界に廃棄された場合には、分解されず半永久的に
残存し環境を著しく悪化させている。[Prior Art] In recent years, environmental pollution caused by plastic waste has become a serious social problem. In other words, plastics, which are used in large quantities for various purposes including packaging materials, have excellent mechanical strength and durability, but if disposed of in nature after use, they do not decompose. It remains semi-permanently and is seriously deteriorating the environment.
こうした状況のもと、土壌あるいは海水等に存在する微
生物によって分解可能な、いわゆる生分解性ポリマーに
大きな期待が寄せられており、現在いくつかのものが開
発されるに至っている。Under these circumstances, there are great expectations for so-called biodegradable polymers that can be decomposed by microorganisms present in soil, seawater, etc., and several polymers have now been developed.
その中で、例えば特開平２−６６８９号公報に掲載され
ているセルロース系繊維とキトサンとを複合させたフィ
ルムは、乾燥状態のみならず水中においてさえも良好な
機械的強度を有し、また、素材が天然物であるために、
分解性は勿論のこと、分解後に及ぼす自然界への影響も
問題なく、早期実用化が期待されている。Among them, for example, a film made of a composite of cellulose fiber and chitosan published in JP-A-2-6689 has good mechanical strength not only in a dry state but also in water, and Because the material is a natural product,
Not only is it easy to decompose, but it also has no impact on the natural world after decomposition, and is expected to be put to practical use soon.
しかしながら、上記セルロース系繊維とキトサンの複合
フィルムを成形する場合、キトサンに熱可望性がないた
めに溶液流延法が適用されるが、キトサン？８ｆ！ｉ、
自体が比較的高粘度であるうえ、径の小さいセルロース
系繊維を多量にキトサン／８液に分散させた製膜原液は
非常に高粘度となるため、溶液流延に適した粘度を有す
る原液を得ようとすると、原液濃度は極めて低いものと
なり、そのため乾燥に著しく長時間を要し、工業的に生
産することは困難である。However, when forming a composite film of the above-mentioned cellulose fibers and chitosan, a solution casting method is applied because chitosan has no thermal stability, but chitosan? 8f! i,
In addition to having a relatively high viscosity, the film-forming stock solution in which a large amount of small-diameter cellulose fibers are dispersed in the chitosan/8 solution has a very high viscosity. When attempting to obtain such a product, the concentration of the stock solution is extremely low, and therefore drying takes an extremely long time, making it difficult to produce it industrially.
また、比較的径の大きなセルロース繊維を使用した場合
には、濃度の高い製膜原液を得ることができるが、フィ
ルム中のキトサン分量が低いと、セルロース繊維の剛性
が高いために乾燥後のフィルム中に空隙を生し、フィル
ム強度は著しく低いものとなる。フィルム中のキトサン
分量を相当高くすればこの問題は解決するが、耐水強度
が低下し問題である。In addition, when cellulose fibers with relatively large diameters are used, it is possible to obtain a highly concentrated film-forming stock solution, but if the amount of chitosan in the film is low, the rigidity of the cellulose fibers is high, resulting in a film after drying. Voids are formed inside the film, and the film strength becomes extremely low. This problem can be solved by increasing the amount of chitosan in the film, but the water resistance is reduced, which is a problem.
本発明は、セルロース系繊維とキトサンの複合フィルム
の上記問題を解決し、機械的強度、生分解性および工業
的生産性ともに良好な生分解性フィルムを得ることを目
的とするものである。The present invention aims to solve the above-mentioned problems of composite films of cellulose fibers and chitosan, and to obtain biodegradable films with good mechanical strength, biodegradability, and industrial productivity.
〔問題を解決するだめの手段］
本発明者らは、かかる状況に鑑み種々検討した結果、短
径が２０ミクロン以下でかつ短径と長径の比が１０以下
である粉末状のセルロースおよび／またはコメデンプン
粒と、セルロースもしくはコメデンプン粒または両者の
合計量１００重量部に対し５〜１００重量部のキトサン
とからなるフィルムが、目的とする生分解性フィルムと
して最適であることを見い出し、本発明を完成するに至
った。[Means for Solving the Problem] As a result of various studies in view of the above situation, the present inventors have found that powdered cellulose and/or It has been discovered that a film consisting of rice starch granules and 5 to 100 parts by weight of chitosan per 100 parts by weight of cellulose, rice starch granules, or both is optimal as the desired biodegradable film, and the present invention I was able to complete it.
〔発明の構成］
本発明における粉末状のセルロースは、パルプを機械的
あるいは化学的処理により粉末化したもののうち、短径
が２０ミクロン以下、好ましくは２〜１５ミクロンであ
り、かつ短径と長径の比が１０以下であるものが使用さ
れる。この形状の粉末状セルロースは、キトサン／８液
中に分散しても粘度上昇が少なく、製膜原液の濃度を高
くすることができる。また、フィルム中での充填性も良
好であり、緻密で強度の高いフィルムを得ることができ
る。[Structure of the Invention] The powdered cellulose in the present invention is obtained by pulverizing pulp by mechanical or chemical treatment, and has a short axis of 20 microns or less, preferably 2 to 15 microns, and a short axis and a long axis. Those having a ratio of 10 or less are used. Powdered cellulose in this shape shows little increase in viscosity even when dispersed in the chitosan/8 solution, and the concentration of the membrane-forming stock solution can be increased. Moreover, the filling properties in the film are good, and a dense and strong film can be obtained.
また、コメデンプン粒はその形状が直径５ミクロン前後
の球形のものが好適であり、上記形状のセルロースと同
様に原液の粘度上昇もなく、また、フィルム中での充填
性も良好である。本発明では、コメデンプンは糊化せず
粒子の状態で使用する。In addition, rice starch particles are preferably spherical in shape with a diameter of about 5 microns, and like cellulose having the above shape, there is no increase in the viscosity of the stock solution, and the filling property in the film is also good. In the present invention, rice starch is used in the form of particles without gelatinization.
コメ以外の植物に由来する例えばトウモロコシデンプン
、ハレイショデンプン等も使用可能であるが、いずれも
粒子径が大きいために、フィルム化した場合内部に空洞
が生じて強度が低下するほか、フィルム部の表面平滑性
も悪いものとなるため、これらのデンプンを使用する場
合、本発明ではコメデンプンに対して２０重量％以下に
止めるのが望ましい。It is also possible to use corn starch, potato starch, etc. derived from plants other than rice, but since both have large particle sizes, when formed into a film, cavities are formed inside and the strength is reduced. Since the surface smoothness is also poor, when these starches are used, it is desirable in the present invention to limit the amount to 20% by weight or less based on the rice starch.
上記粉末状セルロースおよびコメデンプンは、いずれも
低コストであるため、経済性からみてもフィルム構成材
として好ましい。The above-mentioned powdered cellulose and rice starch are both low-cost and are therefore preferable as film constituent materials from an economic standpoint.
本発明におけるキトサンは、カニ、エビ等の甲殻類の外
殻に含有されるキチンを、濃アルカリ処理によって脱ア
セチル化したものである。キトサンの脱アセチル化度に
特に限定はないが、通常７０〜９５モル％のものが使用
される。フィルム中のキトサンの量は、セルロースおよ
び／またはデンプン１００重量部に対し５〜１００重量
部、さらに好ましくは１５〜５０重量部が良い。キトサ
ン量がこの範囲よりも少ない場合には、セルロースやコ
メデンプン粒間に空洞が生し強度が低下し、一方、多い
場合には水中強度が低下し問題であるうえ、キトサンは
比較的高価であるため経済性が低下する。Chitosan in the present invention is obtained by deacetylating chitin contained in the outer shell of crustaceans such as crabs and shrimps by treating with a concentrated alkali. Although there is no particular limitation on the degree of deacetylation of chitosan, a degree of deacetylation of 70 to 95 mol% is usually used. The amount of chitosan in the film is preferably 5 to 100 parts by weight, more preferably 15 to 50 parts by weight, based on 100 parts by weight of cellulose and/or starch. If the amount of chitosan is less than this range, cavities will be formed between the cellulose and rice starch particles, resulting in a decrease in strength.On the other hand, if the amount is too much, the strength in water will decrease, which is a problem, and chitosan is relatively expensive. Therefore, economic efficiency decreases.
また、本発明では上記構成物質のほか、フィルムの柔軟
性を改善する目的で、グリセリン、エチレングリコール
、ジエチレングリコール、プロピレングリコール、ソル
ビトール等の多価アルコールを添加することが有効であ
る。さらにに、離型剤、分散安定剤、ブロッキング防止
剤、着色剤等を添加しても差し支えない。Furthermore, in the present invention, in addition to the above constituent substances, it is effective to add polyhydric alcohols such as glycerin, ethylene glycol, diethylene glycol, propylene glycol, and sorbitol for the purpose of improving the flexibility of the film. Furthermore, a mold release agent, a dispersion stabilizer, an antiblocking agent, a coloring agent, etc. may be added.
本発明による生分解性フィルムを工業的に製膜するには
、例えばまず、キトサンを酢酸等の酸性水溶液に溶解し
、そこに所定量の粉末状セルロースもしくはコメデンプ
ン粒、または粉末状セルロースおよびコメデンプン粒を
均一に分散させて製膜原液とし、これを金属製のドラム
、あるいはエンドレスヘルド等の乾燥面に流延し、乾燥
同化後形成したフィルムを乾燥面より剥離すれば良い。To industrially form the biodegradable film of the present invention, for example, first, chitosan is dissolved in an acidic aqueous solution such as acetic acid, and a predetermined amount of powdered cellulose or rice starch granules, or powdered cellulose and rice is added thereto. Starch granules may be uniformly dispersed to form a film-forming stock solution, which may be cast onto a drying surface of a metal drum or endless heald, and after drying and assimilation, the formed film may be peeled off from the drying surface.
本発明では、高濃度の原液を調製できるため、乾燥は短
時間で完了し、極めて容易に工業的製膜が実施できる。In the present invention, since a highly concentrated stock solution can be prepared, drying can be completed in a short time and industrial film formation can be carried out extremely easily.
本発明によるフィルムは、同様にして製膜したキトサン
単体フィルムが水に溶解するのに対し、製膜後にアルカ
リ処理を施さな（でも良好な水中強度を有している。し
かしながら、キトサンと複合化させる物質がコメデンプ
ン粒単独の場合は、セルロース単独の場合と比較して水
中でのフィルム強度が低いため、特に高い耐水性が必要
な場合はセルロースと併用するのが好ましい。The film according to the present invention has good strength in water even though it is not subjected to alkali treatment after film formation (although chitosan alone dissolves in water). When rice starch granules alone are used as the substance, the film strength in water is lower than when cellulose alone is used, so it is preferable to use them together with cellulose when particularly high water resistance is required.
本発明によるフィルムは、′土壌中あるいは海洋や河川
等に投棄された場合には、容易に微生物によって分解さ
れ、また、構成物質がすべて天然物であるため分解後も
環境に悪影響を及ぼす心配はない。The film according to the present invention is easily decomposed by microorganisms when it is disposed of in the soil or in the ocean or river, and since all of its constituent materials are natural products, there is no need to worry about it having a negative impact on the environment even after decomposition. do not have.
以上のように、本発明による生分解性フィルムは優れた
機械的強度、化分解性、経済性を有するうえ、工業的製
膜も容易であり、各種包装用フィルム、回収不要の農業
用フィルム等に有用である。As described above, the biodegradable film according to the present invention has excellent mechanical strength, chemical degradability, and economic efficiency, and is also easy to produce on an industrial scale, and can be used as a variety of packaging films, agricultural films that do not require collection, etc. It is useful for
以下に実施例を示し、本発明およびその効果を具体的に
説明する。EXAMPLES The present invention and its effects will be specifically explained below with reference to Examples.
実施例１
脱アセチル化度が８４モル％のキトサンを１．７重量％
の酢酸水溶液に５重量％溶解した溶液と、短径が１７ミ
クロン以下で短径と長径の比が５以下である粉末状セル
ロース（ドイツＪ、 Ｒｅｔｔｅｎｍａｉｅｒ ＆Ｓろ
ｈｎｅ社製、ＡＲＢＯＣＥＬ ＢＥ６００／３０）の２
５重量％の水分散液およびグリセリンを良く混合し、製
膜原液を調製した。セルロース；キトサン：グリセリン
の重置比ば１００ ： ３０ ： ５０とした。この原
液の濃度は約２０重量％であり、また、溶液流延に適し
た粘度を有していた。Example 1 1.7% by weight of chitosan with a degree of deacetylation of 84 mol%
A solution of 5% by weight dissolved in an acetic acid aqueous solution of 2
A 5% by weight aqueous dispersion and glycerin were thoroughly mixed to prepare a membrane forming stock solution. The superposition ratio of cellulose: chitosan: glycerin was 100:30:50. The concentration of this stock solution was about 20% by weight, and the viscosity was suitable for solution casting.
二の原液を８０°Ｃ４こ加温したクロムメツキ鋼板上に
流延し、表面に１００°Ｃの熱風を当てて乾燥し、厚さ
６０ミクロンのフィルムを作成した。乾燥Ｏこ要した時
間は約１分であった。The second stock solution was cast onto a chrome-plated steel plate heated to 80°C, and the surface was dried by blowing hot air at 100°C to form a film with a thickness of 60 microns. The time required for drying was about 1 minute.
このフィルムは表面が平滑でしなやかなフィルムであり
、顕微鏡によりフィルム表面を観察したところ、第１図
に示すように、セルロースが緻密に充填されており空洞
は見られなかった。２０°Ｃ６０％ＲＨにおける引張強
度（以下乾燥強度と言う）は２３０ｋｇｆ／ｃｉｉ、ま
た、２０゛Ｃの水に２４時間浸漬した時の引張強度（以
下水中強度と言う）は８０ｋｇｆ／ｃｍと良好な強度を
有していた。This film had a smooth and flexible surface, and when the surface of the film was observed under a microscope, as shown in FIG. 1, it was found that cellulose was densely packed and no cavities were observed. The tensile strength at 20°C and 60%RH (hereinafter referred to as dry strength) is 230kgf/cii, and the tensile strength when immersed in water at 20°C for 24 hours (hereinafter referred to as underwater strength) is 80kgf/cm. It had strength.
このフィルムを畑より採取した含水率約２０％、温度約
２０°Ｃの土壌中に埋没させたところ、約４週間で原形
をまったく留めないまでに分解した。また、このフィル
ムを金網に挟み係留中の釣船の生けすに吊し、春季に海
水での分解性を調べたところ、６週間で分解消失した。When this film was buried in soil collected from a field with a moisture content of about 20% and a temperature of about 20°C, it decomposed in about 4 weeks without retaining its original shape at all. In addition, this film was sandwiched between wire mesh and hung in a cage on a moored fishing boat, and its decomposition properties in seawater were examined in the spring, and the film decomposed and disappeared within 6 weeks.
実施例２
脱アセチル化度が７９モル％のキトサンを、１．２重置
％の酢酸水溶液に３．５重量％溶解した溶液に、コメデ
ンプン粒およびグリセリンを添加し、良く攪拌混合して
製膜原液を調製した。コメデンプン粒：ギトサン：グリ
セリンの重量比をｔｏｏ ： ５０ ニア５としたこの
原液の濃度は約１４重量％であった。Example 2 Rice starch granules and glycerin were added to a solution of 3.5% by weight of chitosan with a degree of deacetylation of 79 mol% dissolved in a 1.2% acetic acid aqueous solution, and the mixture was thoroughly stirred and mixed. A membrane stock solution was prepared. The concentration of this stock solution was about 14% by weight, with the weight ratio of rice starch granules: Gitosan: Glycerin being too: 50 near 5.
この原液より、実施例１と同様の方法で、厚さ４０ミク
ロンのフィルムを作成したところ、乾燥は約１分で完了
した。作成したフィルムは、表面平滑性の良好な半透明
なフィルムであり、乾燥強度は１４０Ｋｇｆ／ｃ＋ａ、
水中強度は５５Ｋｇｆ／ｃｆｆｌであった。また、土壌
中、γ復水中の分解時間は、それぞれ３週間、６週間と
良好であった。A film with a thickness of 40 microns was prepared from this stock solution in the same manner as in Example 1, and drying was completed in about 1 minute. The produced film is a translucent film with good surface smoothness, and has a dry strength of 140 Kgf/c+a.
The underwater strength was 55Kgf/cffl. In addition, the decomposition times in soil and gamma condensate were good, 3 weeks and 6 weeks, respectively.
実施例３
実施例１のフィルム作成法に準し、セルロース；コメデ
ンプン粒：キトサン：グリセリンの比が５０：５０ ：
２０ ： ３５のフィルムを作成した。このときの製
膜原液の濃度は約２３％であり、実施例１と同様に乾燥
も極めて短時間で完了した。Example 3 According to the film making method of Example 1, the ratio of cellulose: rice starch granules: chitosan: glycerin was 50:50:
A film with a ratio of 20:35 was produced. The concentration of the membrane forming stock solution at this time was about 23%, and as in Example 1, drying was completed in an extremely short time.
このフィルムも実施例１と同様に良好な外観を有し、乾
燥強度は２５０ｋｇｆ／ｃｄ、水中強度は６５ｋｇｆ／
ｃ＋＋１であった。また、土壌中および海水中の分解性
も良好であった。This film also has a good appearance like Example 1, has a dry strength of 250 kgf/cd, and an underwater strength of 65 kgf/cd.
It was c++1. Furthermore, the degradability in soil and seawater was also good.
比較例１
セルロースとして、短径が約２０ミクロンで短径と長径
の比が２０以上の形状を有するものを多量に含有する粉
末状セルロース（山場国策パルプ社製、パルプフロック
−１）を使用した以外は、実施例１と同様であるフィル
ムを作成した。濃度２０重量％で調製した原液は溶液流
延に適した粘度を有しており、乾燥時間も問題なかった
が、フィルムの表面性は非常に悪く、また、乾燥強度が
４５ｋｇｆ／ｃ＋１１゜水中強度が２２ｋｇｆ／ｃｄと
極めて強度の弱いフィルムであった。フィルム表面を顕
微鏡で観察すると、第２図に示すように、セルロース間
に多くの空洞が見られた。Comparative Example 1 Powdered cellulose (manufactured by Yamaba Kokusaku Pulp Co., Ltd., Pulp Flock-1) containing a large amount of cellulose having a short axis of about 20 microns and a ratio of short axis to long axis of 20 or more was used as cellulose. A film similar to Example 1 was produced except for this. The stock solution prepared at a concentration of 20% by weight had a viscosity suitable for solution casting, and there was no problem with the drying time, but the surface properties of the film were very poor, and the dry strength was 45 kgf/c + 11° underwater strength. The film had an extremely low strength of 22 kgf/cd. When the film surface was observed under a microscope, many cavities were observed between the cellulose, as shown in FIG.
比較例２
コメデンプン粒の代わりに、トウモロコノデンプン粒を
使用した以外は、実施例２と同様であるフィルムを作成
した。このフィルムは表面がざらざらであり、乾燥強度
は６５ｋｇｆ／ｃＩＩＩ、水中強度は３２ｋｇｆ／ｃｄ
であり、コメデンプンの場合と比較して著しく強度が低
下した。Comparative Example 2 A film similar to Example 2 was prepared except that corn starch granules were used instead of rice starch granules. This film has a rough surface and has a dry strength of 65 kgf/cIII and an underwater strength of 32 kgf/cd.
The strength was significantly lower than that of rice starch.
比較例３
粉末状セルロースの代わりに、微細に叩解したいわゆる
ミクロフィブリルセルロース（ダイセル化学工業社製、
ＭＦＣ）を使用し、実施例１と同し組成のフィルムを作
成した。ミクロフィブリルセルロースは、高濃度で水中
に分散させると流動性が消失するため、その取り扱い上
キトサン？８液と混合する際の濃度は２％としたが、調
製後の原ｔａ度は３．３％と極めて低いものとなった。Comparative Example 3 Instead of powdered cellulose, finely beaten so-called microfibril cellulose (manufactured by Daicel Chemical Industries, Ltd.,
A film having the same composition as in Example 1 was prepared using MFC). Microfibrillar cellulose loses its fluidity when dispersed in water at high concentrations, so it is difficult to handle it with chitosan. Although the concentration when mixing with Liquid 8 was 2%, the raw tatness after preparation was extremely low at 3.3%.
この原液より実施例１と同様な方法で厚みが６０ミクロ
ンのフィルムを作成したところ、原液の流延膜厚が非常
に厚いものとなり、乾燥には約１２分と極めて長時間を
要したうえ、作成したフィルムの厚みは不均一であった
。When a film with a thickness of 60 microns was created from this stock solution in the same manner as in Example 1, the cast film thickness of the stock solution was very thick, and it took an extremely long time to dry, about 12 minutes. The thickness of the produced film was non-uniform.
第１図および第２図は、それぞれ実施例１および比較例
Ｉにより作成されたフィルム表面の走査電子顕微鏡写真
である。
出願人 工業技術院長 杉浦 賢
〃 アイセロ化学株式会社FIGS. 1 and 2 are scanning electron micrographs of the surfaces of films prepared in Example 1 and Comparative Example I, respectively. Applicant Ken Sugiura, Director of the Agency of Industrial Science and Technology Aicello Chemical Co., Ltd.
Claims (1)
下である粉末状のセルロースおよび／またはコメデンプ
ン粒と、セルロースもしくはコメデンプン粒または両者
の合計量１００重量部に対し５〜１００重量部のキトサ
ンとからなることを特徴とする生分解性フィルム。Powdered cellulose and/or rice starch granules with a short axis of 20 microns or less and a ratio of short axis to long axis of 10 or less, and 5 to 100 parts by weight per 100 parts by weight of the total amount of cellulose or rice starch granules, or both. A biodegradable film characterized by comprising part of chitosan.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33605890A JPH0774279B2 (en) | 1990-11-30 | 1990-11-30 | Biodegradable film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33605890A JPH0774279B2 (en) | 1990-11-30 | 1990-11-30 | Biodegradable film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04202436A true JPH04202436A (en) | 1992-07-23 |
| JPH0774279B2 JPH0774279B2 (en) | 1995-08-09 |
Family
ID=18295264
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33605890A Expired - Lifetime JPH0774279B2 (en) | 1990-11-30 | 1990-11-30 | Biodegradable film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0774279B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103450507A (en) * | 2013-08-23 | 2013-12-18 | 吴江市英力达塑料包装有限公司 | Chitosan composite film and preparation method thereof |
| JP2021526561A (en) * | 2018-03-13 | 2021-10-07 | アルベルト−ルートヴィヒ−ウニヴェルズィテート フライブルク | Aqueous gel complex containing chitosan and cellulose nanofibers |
| WO2024048402A1 (en) * | 2022-08-29 | 2024-03-07 | 三菱ケミカル株式会社 | Resin composition containing biodegradable resin |
-
1990
- 1990-11-30 JP JP33605890A patent/JPH0774279B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103450507A (en) * | 2013-08-23 | 2013-12-18 | 吴江市英力达塑料包装有限公司 | Chitosan composite film and preparation method thereof |
| JP2021526561A (en) * | 2018-03-13 | 2021-10-07 | アルベルト−ルートヴィヒ−ウニヴェルズィテート フライブルク | Aqueous gel complex containing chitosan and cellulose nanofibers |
| WO2024048402A1 (en) * | 2022-08-29 | 2024-03-07 | 三菱ケミカル株式会社 | Resin composition containing biodegradable resin |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0774279B2 (en) | 1995-08-09 |
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